Copolymers of 3, 4, 5, 5, 5-penta-fluoropentadiene-1, 3



United States Patent 3,308,106 COPOLYMERS 0F 3,4,5,5,5-PENTA-FLUOROPENTADIENE-1,3 Anthony J. Butler, George A. Grindahl, and Ogden R.

Pierce, Midland, Mich., assignors to Dow Corning Corporation, Midland,Mich., a corporation of Michigan No Drawing. Filed Jan. 9, 1964, Ser.No. 336,623 6 Claims. (Cl. 260-855) This application relates to new,fluorinated copolymers that vary from tough, flexible, leathery plasticsto elastomers, and which are highly stable in the presence of heat orsolvents.

The copolymers of this invention consists essentially of (1) units and(2) at least one unit selected from the group consisting of units, whereX is selected from the group consisting of fluorine and hydrogen, atleast one X being hydrogen, R is selected from the group consisting offluorine, hydrogen and perfluoroalkyl radicals, and R is selected fromthe group consisting of the trifluoromethyl radical and fluorine, thenumber of Xs that are hydrogen exceeding the number of Rs that arehydrogen;

where Z is selected from the group consisting of the trifluoromethylradical, fluorine, and hydrogen, X is selected from the group consistingof fluorine and hydrogen, and R is as defined above,

CX2(IJQ,'

units; where X is as defined above, and Q is selected from the groupconsisting of hydrogen, fluorine, and methyl, there being at least one Hatom present; and

Patented Mar. 7, 1967 ice where the symbols are as defined above.

The copolymerization may be conveniently effected by emulsifying theingredients and using a redox initiation,

as in Example 2.

Ingredients (1) of the copolymers of this invention can be made byreacting perfluoropropene with ethanol, using a free radical catalyst:

CF3CF=CF2 CHaCHzOH The various compounds that can make up ingredient 2)are well known to the art.

It should be noted that the polymerization of ingredient (1) takes placeonly on the terminal double bond. This leaves olefinic pendant groupsalong the main chain. It should also be noted that the ingredients (2)can have pendant groups.

More than one species of ingredient (2) can be used if it is desired tomake a copolymer with more than tWo types of polymeric units therein.

The preferred ingredient 2) is CRR'=CRCX=CX The following examples areillustrative only and should not be construed as limiting the inventionwhich is properly delineated in the appended claims.

Example 1 0.15 gram of K S O 0.08 gram of sodium bisulfite, 0.008 gramof FeSO '7H O, and 0.5 gram of potassium perfluorooctoate were placed asa dry powder into a polymer tube. After purging with nitrogen andcooling the tube, 32 grams of Water buffered at a pH of 10, 9 grams of3,4,5,5,S-pentafluoropentadiene-1,3 and 9 grams ofvinylpentafluorobenzene was added. The N pressure in the tube was thenadjusted to atmospheric pressure for ease in sealing. The tube wasplaced in a vented steel jacket and agitated mildly in a hot water bath(45 C.) for 20 hours. The tubes were then frozen and the poly merremoved, coagulated, and washed with warm water. It was then dried inwarm air.

The product was a copolymer consisting essentially of units and units. I

Example 2 The following were placed in a glass polymerization arnpule:0.1 gram of K S O 0.05 gram of sodium bisul fite, 0.005 gram of FeSO -7HO, 0.5 gram of C7F15COOK, 32 grams of water, buffered at pH 10, 5 gramsof CF =CHCH=CH and 10 grams of 3 4 The tubes were sealed and left in DryIce overnight. units and The tubes were then rotated in a hot water bathat 50 C. for about twenty hours. F The product was an emulsion, with noexcess monomer H detectable. It was found to contain a copolymerconsist- 5 z ing essentially of units. It was a snappy and very strongelastomer.

-(IJHCH2 Example 4 The following were placed in a glass polymerizationCF ampule: 0.15 gram K S O 0.08 gram sodium bisulfite, 0.008 gram FeSO'7H O, 0.5 gram C F COOK, 40 grams d of water buffered at pH 10, 14grams of units an CF CF CFCH=CH CHCII2 I 15 and 10 grams of CH CHCN. Thetube was agitated in H a hot water bath for 18 hours. The product was anex- CFZ panded, solid copolymer consisting essentially of --(|/HCH2units.

0 F Example 3 20 t. The following were placed in a glass polymerization([3173 ampule: 0.1 gram of K S O 0.05 gram of sodium bisulit d fite,0.005 gram of FeSO -7H O, 0.6 gram of C7F 5cOOK, -OHGIL- 32 grams ofwater buffered at pH 10, 15 grams of CRCF CFCH CH and 6 grams of unitsCF CFCH CH After washing with methanol and oven drying, the co- Ipolymer was a white, thermoplastic powder. The ampule Was placed 1n ahot water bath at 50 C. for about 18 hours. Example 5 The product waswashed in a mixture of methanol, When the following compounds arecopolymerized with water, and acetone, and then with Water. It was thenCF CF CFCH=CH in the mol ratios stated in accorddried for 3 hours at 110C. ance with the method of Example 1, copolymers contain- T he productwas a copolyrner consisting essentially of ing (A) CHCH2 (|3HCH2- F r F40 0 F3 CFK units, and (B) the following units are obtained.

M01 Percent Compound Copolymer Unit 13 M01 Percent A Mol Percent B 5oF3oF2C-F=CFOF=CHF -CF-CHF- 95 5 'C F CF-CFzCF;

0R CI'I-C F2 1 C1uF2iCF CCH=CFz CF3C 99 1 CFC10F21 (|3F(CF3)2 CFCH: 99(CF3)C=COF=CH2 C-OF(CF3)z 1 90 C (fHa CH3 35 OFH=OCN CFH( 3 35 50CF3=OI-ICN CF2CH 50 50 25 CH2=CFCN -CHz(fF- 25 60 OHz=CFCF=CHzOI-IZCF=CFCHZ 40 60 so oHF=oFOF=oI-IF -OHFCF=CF-OHF 20 0 (1H3 F CH3 10CHFC CFa CH2(|3- 10 CF3 F F F F F CF Example 6 When CF CF=CFCH=CH iscopolymerized in accordance with the method of Example 1 with CFCFCF=CH-CH=CH and CHFCH a copolymer is formed consisting essentially ofCHCH2 units,

units, and

-CH2C H- units.

That which is claimed is: 1. A copolymer consisting essentially of (1)-CHCH2 units and (2) at least one unit selected from the groupconsisting of CXCX2 units, where X is selected from the group consistingof fluorine and hydrogen, at least one X being hydrogen, R is selectedfrom the group consisting of fluorine, hydrogen, and perfluoroalkylradicals, and R is selected from the group consisting of thetrifluoromethyl radical and fluorine, the number of Xs that are hydrogenexceeding the number of Rs that are hydrogen;

CRZ--CF=CF-CX where Z is selected from the group consisting of thetrifluoromethyl radical, fluorine, and hydrogen, X is selected from thegroup consisting of fluorine and hydrogen, and R is as defined above;

units, where X is as defined above, and Q is selected from the groupconsisting of hydrogen, fluorine and methyl; and

units, where Q' is selected from the group consisting of thetrifluoromethyl radical and fluorine, no more than two Q groups beingtrifluoromethyl, and Y is selected from the group consisting of methylradicals and hydrogen.

2. A copolymer consisting essentially of from 5 to mol percent of (1)units, and from 95 to 5 mol percent of (2) units selected from the groupconsisting of units, where X is selected from the group consisting offluorine and hydrogen, at least one X being hydrogen;'R is selected fromthe group consisting of fluorine, hydrogen and perfluoroalkyl radicals,and R is selected from the group consisting of the trifluoromethylradical and fluorine, the number of Xs that are hydrogen exceeding thenumber of Rs that are hydrogen;

where Z is selected from the group consisting of the trifluoromethylradical, fluorine, and hydrogen, X is selected from the group consistingof fluorine and hydrogen, and R is as defined above;

95 mol percent of -OHCH2 units and from 95 to 5 mol percent of CHCH2 FI! CF2 units.

4. A copolymer consisting essentially of 5 to 95 mol percent of OHCHz(1F JlF J a units and 95 to 5 mol percent -oHcHi units.

7 8 5. A copolymer consisting essentially of 5 to 95 mol 6. A copolymerconsisting essentially of 5 to 95 mol percent of p rcent Of -(|3HOH2 CFCII-OHz 5 ll CF F I a. r units and 95 to 5 mol percent of C 3 10 C|7HCH2n C z units.

units and 95 to 5 mol percent of 15 No references cited.

CHCH2- JOSEPH L. SCHOFER, Primary Examiner.

units. HARRY WONG, Assistant Examiner.

1. A COPOLYMER CONSISTING ESSENTIALLY OF (1)